EP0718301B1 - A silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it - Google Patents

A silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it Download PDF

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EP0718301B1
EP0718301B1 EP95120442A EP95120442A EP0718301B1 EP 0718301 B1 EP0718301 B1 EP 0718301B1 EP 95120442 A EP95120442 A EP 95120442A EP 95120442 A EP95120442 A EP 95120442A EP 0718301 B1 EP0718301 B1 EP 0718301B1
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trans
group
liquid crystal
silacyclohexyl
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EP0718301A1 (en
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Takaaki Shimizu
Ogihara Tsutomu
Asakura Kazuyuki
Kinsho Takeshi
Kaneko Tatsushi
Nakashima Mutsuo
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Shin Etsu Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
    • C09K19/406—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing silicon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides

Definitions

  • This invention relates to a new silacyclohexane compound, a method of preparing it, and a liquid crystal composition which contains it, as well as a liquid crystal display element containing said liquid crystal composition.
  • a liquid crystal display element utilizes the optical anisotropy and dielectric anisotropy of liquid crystal substances.
  • Display methods include the TN mode (twisted nematic mode), the STN mode (super twisted nematic mode), the SBE mode (super birefringence mode), the DS mode (dynamic scattering mode), the guest-host mode, the DAP mode ("deformation of aligned phase” mode) and the OMI mode (optical mode interference mode).
  • the most common display device has a twisted nematic structure based on the Schadt-Helfrich mode.
  • liquid crystal substance used in these liquid crystal displays are somewhat different depending on the display method. However, a wide liquid crystal temperature range and stability with regard to moisture, air, light, heat, electric fields, etc., are properties commonly required by all display methods. Furthermore, it is desirable for the liquid crystal material to have a low viscosity, and also to have a short address time, low threshold voltage and high contrast in the cell.
  • liquid crystal mixtures are used which are obtained by mixing several to more than ten liquid crystal compounds and latent liquid crystal compounds. Because of this, it is also important that the components of a liquid crystal composition mix easily.
  • liquid crystal compounds which can be components of these are classified into several categories based on their functions, as shown below:
  • one of the basic components conventionally known which controls the electro-optical performance is a compound which has a so-called cyclohexyl ring-cyclohexyl ring-phenyl structure (CCP structure) with a mono- or di-fluoroalkyl chain(s) such as: (Japanese unexamined patent publication Tokkai Hei 6-184019) and (Tokkai Hei 6-192142).
  • the object of the invention is to provide a newly developed liquid crystal substance with the PCH structure containing a silacyclohexane ring, targeting improvement in the characteristics of "1) compounds which contribute to a reduction in viscosity and a lowering of the melting point of the mixed liquid crystal composition".
  • the other object of the invention is to provide a newly developed liquid crystal substance with the aforementioned cyclohexyl ring-cyclohexyl ring-phenyl structure (CCP structure).
  • This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) characterized by the use of a reaction between an organo- metallic reagent R-M (M denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound: wherein W denotes H, F, Cl or a CH 3 group. Q denotes a halogen or an alkoxy group.
  • R-M organo- metallic reagent
  • R-M M denotes MgP (P denotes a halogen), ZnP or Li
  • W denotes H, F, Cl or a CH 3 group.
  • Q denotes a halogen or an alkoxy group.
  • This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) characterized by the use of a reaction between an organo-metallic reagent: and a silacyclohexane compound:
  • This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) wherein X is CN, characterized by the use of a reaction between an organometallic reagent: (wherein M denotes MgP' (P' denotes Br or I), Zn or Li, and X ' denotes a halogen) and a silacyclohexane compound: to obtain a phenylsilacyclohexane compound: from which a Grignard's reagent is made, which is then reacted with a cyanogenation agent.
  • organometallic reagent wherein M denotes MgP' (P' denotes Br or I), Zn or Li, and X ' denotes a halogen
  • This invention in another aspect provides a silacyclohexane compound represented by the following general formula (II): wherein R denotes hydrogen or a mono- or di-fluoroalkyl group with 1-10 carbons; and at least one of the two denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH 3 and the other denotes a trans-1, 4-cyclohexylene group, a trans-1-silacyclohexylene group or a trans-4-silacyclohexylene group;
  • This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (II) characterized by the use of a reaction between an organometallic reagent R-M (M denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound: wherein W denotes H, F, Cl or a CH 3 group, and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.
  • R-M organometallic reagent
  • R-M M denotes MgP (P denotes a halogen), ZnP or Li
  • W denotes H, F, Cl or a CH 3 group
  • Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.
  • This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (II) characterized by the use of a reaction between an organometallic reagent: and a silacyclohexane compound: wherein: denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH 3 , or a cyclohexylene group; W denotes H, F, Cl or a CH 3 group; and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.
  • This invention also provides a liquid crystal composition characterized by containing the silacyclohexane compound represented by said general formulas (I) or (II), and a liquid crystal display element characterized by containing this liquid crystal composition.
  • R denotes a mono- or difluoroalkyl group with 1-10 carbons, i.e. fluoromethyl, 1-fluoroethyl, 1-fluoropropyl, 1-fluorobutyl, 1-fluoropentyl, 1-fluorohexyl, 1-fluoroheptyl, 1-fluorooctyl, 1-fluorononyl, 1-fluorodecyl, 2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2-fluoropentyl, 2-fluorohexyl, 2-fluoroheptyl, 2-fluorooctyl, 2-fluorononyl, 2-fluorodecyl, 3-fluoropropyl, 3-fluorobutyl, 3-fluoropentyl, 3-fluorohexyl, 3-fluoroheptyl, 3-fluorooctyl, 3-fluorononyl, 3-fluoroprop
  • W, W 1 and W 2 independently denote H, F, Cl or CH 3 .
  • Y denotes H or F.
  • Z denotes H or F.
  • n and m denote an integer of 0-9 where n + m is 1-9.
  • H, F and CH 2 groups are desirable for W in practical use.
  • W is limited to H or a CH 3 group.
  • the compound produced here is a mixture of trans isomers and cis isomers in terms of the configuration of the silacyclohexane ring.
  • a conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (I).
  • the reaction formula is shown below. (P 2 preferably denotes Br or I; X' denotes a halogen which is preferably Cl, Br or I; and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.) (2) A method of preparing the compound of this invention other than (1) as described above.
  • reaction substrates are somewhat different depending on the ring structure, all of them are prepared using the coupling reactions of organometallic reagents shown below.
  • R-halide or substituted aryl halide is used in a solvent such as THF (tetrahydrofuran) to obtain the corresponding organometallic reagent.
  • the organometallic reagent thus produced is then brought into reaction with a silacyclohexane compound whose silicon has the substitutional groups W and Q.
  • the compound produced here is a mixture of trans isomers and cis isomers in terms of the configuration of the silacyclohexane ring.
  • a conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (I).
  • the reaction formula is shown below.
  • ⁇ M denotes MgP 1 (P 1 denotes a halogen which is preferably Cl, Br or I), ZnP 1 or Li; M' denotes Mg (P 2 preferably denotes Br or I (when X is Cl), or Cl, Br or I (when X is not Cl)). ZnP 2 or Li; Q denotes a halogen or alkoxy group with preferably 1-4 carbons; and W denotes a H, F, Cl or CH 3 group.
  • Y denotes H or F.
  • reaction substrates are somewhat different depending on the ring structure, all of them are prepared using the organometallic coupling reactions shown below.
  • P 1 denotes a halogen which is preferably Cl, Br or I;
  • Q denotes a halogen or an alkoxy group with preferably 1-4 carbons,
  • a cyclohexyl halide, R-halide or silacyclohexyl halide in a solvent such as THF (tetrahydrofuran) is used in a conventional manner to obtain the corresponding organometallic reagent.
  • a solvent such as THF (tetrahydrofuran)
  • an appropriate metal species is chosen according to the type of the substitutional group X.
  • the metal halide thus produced is then brought into reaction with a silacyclohexane compound whose silicon has the substitutional groups W or W 2 and Q.
  • the compound produced here is a mixture of trans isomers and cis isomers in terms of the conformation of the silacyclohexane ring.
  • a conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (II).
  • the silacyclohexane compound of this invention can be mixed with known compounds to obtain a liquid crystal composition.
  • the compound used for mixing to obtain the liquid crystals compound can be chosen from among the known compounds shown below:
  • R' denotes hydrogen, a linear-chain alkyl group with 1-10 carbons, a branched-chain alkyl group with 3-8 carbons, an alkoxyalkyl group with 2-7 carbons, a mono- or di- fluoroalkyl group with 1-10 carbons or an alkenyl group with 2-8 carbons.
  • X, Y and Z are the same as defined for the general formulas (I) or (II).
  • the ratio of one or more types of the silacyclohexane compound of this invention contained in the liquid crystal composition is 1-50 mol%, more preferably 5-30 mol%.
  • the liquid crystal composition can also contain a polygenetic dye(s) to generate the colored guest-host system and additives to change the dielectric anisotropy, viscosity and the orientation of the nematic phase.
  • the liquid crystal composition thus formed can be used to manufacture various liquid crystal display elements in conventional methods. That is, the liquid crystal composition containing the silacyclohexane compound of this invention is sealed between transparent plates which have electrodes of desired shapes and thus used as liquid crystal display elements.
  • This element can have various undercoatings, overcoatings for the orientation control, a polarizer plate(s), a filter(s) and a reflector layer(s), as necessary. It can be made into a laminated cell or combined with other display elements. Semiconductor substrates and light sources can also be used to make various types of displays.
  • DSM dynamic scattering
  • TN twisted nematic
  • GH guest-host
  • STN super twisted nematic
  • PDLC polymer dispersion liquid crystal
  • the silacyclohexane compounds of this invention have a strong tendency to show an enantiotropic phase transition when their substitutional group X is CN.
  • substitutional group X is not CN, most of them show a monotropic phase transition or a crystal-isotropic liquid type transition, and do not show the electro-optical characteristics of liquid crystals when used separately. However, they contribute to a reduction in the viscosity and a lowering of the melting point when used with other liquid crystal compounds in a liquid crystal composition.
  • liquid crystal compounds of this invention which have Si as a ring composing element as components of a liquid crystal composition, reduction of the viscosity, improvement of the response time and improvement of compatibility in low temperatures can be achieved.
  • liquid crystal compounds whose X in the general formula (I) is neither R nor OR have, in addition to the advantages mentioned above, an effect of lowering the threshold voltage because of a greater dielectric anisotropy.
  • the liquid crystal compound whose substitutional group X in the general formula (I) is an alkyl group, an alkoxyalkyl group, R or OR has near-zero negative dielectric anisotropy, and therefore it should preferably be used for the liquid crystal phase for display based on the dynamic scattering (DS) or deformation of aligned phase (DAP mode).
  • the compounds in which X is other than an alkyl group, an alkoxyalkyl group, R or OR should preferably be used for manufacturing the liquid crystal phase with a large positive dielectric anisotropy which is used in display elements based on the twisted nematic cell or the cholesteric-nematic phase transition.
  • liquid crystal compounds of the present invention which have Si as a ring composing element have the following advantages over liquid crystal compounds which have a conventional CCP structure comprising similar hydrocarbon rings:
  • liquid crystal compounds whose X in the general formula (II) is neither R nor OR have, in addition to the advantages mentioned above, an effect of lowering the threshold voltage.
  • the threshold voltage can be lowered by increasing the dielectric anisotropy ( ⁇ ) of the liquid crystal compound.
  • the compounds of the present invention have an advantage of having a lower threshold voltage compared with the prior art compounds with the same ⁇ .
  • the liquid crystal compounds of this invention can be widely used as the base material which comprises the major component of the liquid crystal phase, in a manner similar to how the conventional liquid crystal compounds with a CCP structure of similar hydrocarbon rings are used.
  • the liquid crystal compound whose substitutional group X in the general formula : is R or OR has near -zero dielectric anisotropy, and therefore it should preferably be used for the liquid crystal phase for display based on the dynamic scattering (DS) or deformation of aligned phase (DAP mode).
  • the compounds in which X is other than R or OR should preferably be used for manufacturing the liquid crystal phase with a large positive dielectric anisotropy which is used in display elements based on the twisted nematic cell or the cholesteric-nematic phase transition.
  • This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 5.3 g of the trans isomers (yield 92%).
  • This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 6.1 g of the trans isomers (yield 93%).
  • the compounds of this invention obtained in the examples described above were added to existing liquid crystal compositions to prepare liquid crystal compositions of this invention.
  • the threshold voltage and the viscosity at 20 °C were measured.
  • Example 6 The above compound was obtained in the same manner as Example 6, using 4-(3-fluoropropyl)cyclohexylbromide and 4-(4-chloro-4-methyl-4-silacyclohexyl)-1-chloro-2,6-difluorobenzene instead of 4-(4-fluorobutyl) cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
  • This reagent was then dripped into a 50 ml THF solution of 4.7 g (20 mmol) of 4-(4-chloro-4-silacyclohexyl) benzonitrile to obtain 4-(4-(trans-4-n-propylcyclohexyl)-4-silacyclohexyl) benzonitrile.
  • This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 5. 9 g of the trans isomers (yield 83%).
  • This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chroma- tography to obtain 7.4 g of the trans isomers (yield 90%).
  • the above compound was obtained in the same manner as Example 14, using 3-fluoropropylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-fluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
  • the above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-trifluoromethoxybenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
  • the above compound was obtained in the same manner as Example 14, using 3-fluoropropylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-chloro-2-fluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
  • the above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-2,3-difluoro-1-ethoxybenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
  • the above compound was obtained in the same manner as Example 14, using 1-bromopropane and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-(4-fluorobutyl)benzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
  • the above compound was obtained in the same manner as Example 23, using 4-(3-fluoropropyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-n-propylbenzene instead of 4-(4, 4-difluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethoxybenzene, respectively.
  • the above compound was obtained in the same manner as Example 23, using 4-(4-fluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-methyl-4-silacyclohexyl)-1-trifluoromethoxy-2-fluorobenzene instead of 4-(4,4-difluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethoxybenzene, respectively.
  • the compounds of this invention obtained in the examples described above were added to existing liquid crystal compositions to prepare liquid crystal compositions of this invention.
  • the threshold voltage and the transition temperature were measured.
  • a mixture A which comprises 40 moles of 4-(4-(trans-4-ethylcyclohexyl) -trans-4-cyclohexyl)-1, 2-difluor Tavernzene, 35 mol% of 4-(4-(trans-4-n-propylcyclohexyl)-trans-4-cyclohexyl)-1,2-difluorobenzene and 25 mol% of 4-(4-(trans-4-n-pentylcyclohexyl)-trans-4-cyclohexyl)-1,2-difluorobenzene exhibits characteristics listed below.
  • N-I transition temperature 106°C
  • Threshold voltage 2.50 V

Description

This invention relates to a new silacyclohexane compound, a method of preparing it, and a liquid crystal composition which contains it, as well as a liquid crystal display element containing said liquid crystal composition.
The prior Art
A liquid crystal display element utilizes the optical anisotropy and dielectric anisotropy of liquid crystal substances. Display methods include the TN mode (twisted nematic mode), the STN mode (super twisted nematic mode), the SBE mode (super birefringence mode), the DS mode (dynamic scattering mode), the guest-host mode, the DAP mode ("deformation of aligned phase" mode) and the OMI mode (optical mode interference mode). The most common display device has a twisted nematic structure based on the Schadt-Helfrich mode.
The properties required of the liquid crystal substance used in these liquid crystal displays are somewhat different depending on the display method. However, a wide liquid crystal temperature range and stability with regard to moisture, air, light, heat, electric fields, etc., are properties commonly required by all display methods. Furthermore, it is desirable for the liquid crystal material to have a low viscosity, and also to have a short address time, low threshold voltage and high contrast in the cell.
Currently, there is no single compound which satisfies all these requirements. In practice, liquid crystal mixtures are used which are obtained by mixing several to more than ten liquid crystal compounds and latent liquid crystal compounds. Because of this, it is also important that the components of a liquid crystal composition mix easily.
The liquid crystal compounds which can be components of these are classified into several categories based on their functions, as shown below:
  • 1) Compounds which contribute to a reduction in viscosity and a lowering of the melting point of the mixed liquid crystal composition;
  • 2) Compounds which mainly control the electro-optical functions of the mixed liquid crystal composition
  • 3) Compounds which contribute to raising the clearing point of the mixed liquid crystal composition;
  • 4) Compounds which contribute to refraction anisotropy control of the mixed liquid crystal composition; or
  • 5) Compounds which control the colored display and orientation of the mixed liquid crystal composition.
    • For compounds which belong to the category 1) in this classification, compounds with a so-called PCH structure such as:
    Figure 00030001
    (Japanese examined patent publication (Tokko) Sho 56-38146),
    Figure 00040001
    (Tokko Sho 64-373) and
    Figure 00040002
    (Tokko Hei 1-38772) have been known.
    Further, one of the basic components conventionally known which controls the electro-optical performance is a compound which has a so-called cyclohexyl ring-cyclohexyl ring-phenyl structure (CCP structure) with a mono- or di-fluoroalkyl chain(s) such as:
    Figure 00040003
    (Japanese unexamined patent publication Tokkai Hei 6-184019) and
    Figure 00050001
    (Tokkai Hei 6-192142).
    In recent years, along with the expansion of the applications of liquid crystal displays, the characteristics required of liquid crystal materials are becoming more and more advanced and demanding. In particular, superior characteristics such as improved low temperature performance, a wider temperature range for automobile onboard use and a lower driving voltage, compared with conventional liquid crystal substances, are desired.
    Brief Summary of the Invention
    The object of the invention is to provide a newly developed liquid crystal substance with the PCH structure containing a silacyclohexane ring, targeting improvement in the characteristics of "1) compounds which contribute to a reduction in viscosity and a lowering of the melting point of the mixed liquid crystal composition".
    The other object of the invention is to provide a newly developed liquid crystal substance with the aforementioned cyclohexyl ring-cyclohexyl ring-phenyl structure (CCP structure).
    The present invention in one aspect provides a silacyclohexane compound represented by the following general formula (I):
    Figure 00060001
    wherein R denotes a mono- or di-fluoroalkyl group with 1-10 carbons;
    Figure 00060002
    denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3; X denotes a CN, F, Cl, CF3, CF2Cl, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, (O)sCY1=CX1X2 (X1 and Y1 denote H, F or Cl, and X2 denotes F or Cl), (O)sCpHqFr (p denotes 2, 3 or 4, and q and r are integers which satisfy the equation q+r = 2p +1, and s denotes 0 or 1), the aforementioned R, or an alkyl or alkoxy group with 1-5 carbons; Y denotes H or F; and Z denotes H or F.
    This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) characterized by the use of a reaction between an organo- metallic reagent R-M (M denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound:
    Figure 00070001
    wherein W denotes H, F, Cl or a CH3 group. Q denotes a halogen or an alkoxy group.
    This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) characterized by the use of a reaction between an organo-metallic reagent:
    Figure 00070002
    and a silacyclohexane compound:
    Figure 00080001
    This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (I) wherein X is CN, characterized by the use of a reaction between an organometallic reagent:
    Figure 00080002
    (wherein M denotes MgP' (P' denotes Br or I), Zn or Li, and X' denotes a halogen) and a silacyclohexane compound:
    Figure 00080003
    to obtain a phenylsilacyclohexane compound:
    Figure 00090001
    from which a Grignard's reagent is made, which is then reacted with a cyanogenation agent.
    This invention in another aspect provides a silacyclohexane compound represented by the following general formula (II):
    Figure 00090002
    wherein R denotes hydrogen or a mono- or di-fluoroalkyl group with 1-10 carbons;
    Figure 00090003
    and
    Figure 00090004
    at least one of the two denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3 and the other denotes a trans-1, 4-cyclohexylene group, a trans-1-silacyclohexylene group or a trans-4-silacyclohexylene group; X denotes a CN, F, Cl, CF3, CF2Cl, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, (O)sCY1=CX1X2 (X1 and Y1 denote H, F or Cl, and X2 denotes F or Cl), (O)sCpHqFr (p denotes 2, 3 or 4, and q and r are integers which satisfy the equation q+r = 2p+1, and s denotes 0 or 1), a mono- or di-fluoroalkyl group with 1-10 carbons, or an alkyl or alkoxy group with 1-5 carbons; Y denotes H or F; and Z denotes H or F.
    This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (II) characterized by the use of a reaction between an organometallic reagent R-M (M denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound:
    Figure 00100001
    wherein W denotes H, F, Cl or a CH3 group, and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.
    This invention also provides a method of preparing the silacyclohexane compound represented by said general formula (II) characterized by the use of a reaction between an organometallic reagent:
    Figure 00110001
    and a silacyclohexane compound:
    Figure 00110002
    wherein:
    Figure 00110003
    denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3, or a cyclohexylene group; W denotes H, F, Cl or a CH3 group; and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.
    This invention also provides a liquid crystal composition characterized by containing the silacyclohexane compound represented by said general formulas (I) or (II), and a liquid crystal display element characterized by containing this liquid crystal composition.
    Detailed Description
    The present invention is further described in details below.
    The compounds represented by said general formula (I), which have a ring structure with a trans-1 or 4-silacyclohexane ring, are specifically represented by ring structures:
    Figure 00120001
    or
    Figure 00120002
    The new compounds represented by said general formula (II), which have a ring structure with at least one trans -1 or 4-silacyclohexane ring, are specifically represented by ring structures:
    Figure 00130001
    Figure 00130002
    Figure 00130003
    Figure 00130004
    Figure 00140001
    Figure 00140002
    or
    Figure 00140003
    In these formulas, R denotes a mono- or difluoroalkyl group with 1-10 carbons, i.e. fluoromethyl, 1-fluoroethyl, 1-fluoropropyl, 1-fluorobutyl, 1-fluoropentyl, 1-fluorohexyl, 1-fluoroheptyl, 1-fluorooctyl, 1-fluorononyl, 1-fluorodecyl, 2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2-fluoropentyl, 2-fluorohexyl, 2-fluoroheptyl, 2-fluorooctyl, 2-fluorononyl, 2-fluorodecyl, 3-fluoropropyl, 3-fluorobutyl, 3-fluoropentyl, 3-fluorohexyl, 3-fluoroheptyl, 3-fluorooctyl, 3-fluorononyl, 3-fluorodecyl, 4-fluorobutyl, 4-fluoropentyl, 4-fluorohexyl, 4-fluoroheptyl, 4-fluorooctyl, 4-fluorononyl, 4-fluorodecyl, 5-fluoropentyl, 5-fluorohexyl, 5-fluoroheptyl, 5-fluorooctyl, 5-fluorononyl, 5-fluorodecyl, 6-fluorohexyl, 6-fluoroheptyl, 6-fluorooctyl, 6-fluorononyl, 6-fluorodecyl, 7-fluoroheptyl, 7-fluorooctyl, 7-fluorononyl, 7-fluorodecyl, 8-fluorooctyl, 8-fluorononyl, 8-fluorodecyl, 9-fluorononyl, 9-fluorodecyl, 10-fluorodecyl, difluoromethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1-difluorobutyl, 1,1-difluoropentyl, 1,1-difluorohexyl, 1,1-difluoroheptyl, 1,1-difluorooctyl, 1,1-difluorononyl, 1,1-difluorodecyl, 2,2-difluoroethyl, 2,2-difluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 2,2-difluorooctyl, 2,2-difluorononyl, 2,2-difluorodecyl, 3,3-difluoropropyl, 3,3-difluorobutyl, 3,3-difluoropentyl, 3,3-difluorohexyl, 3,3-difluoroheptyl, 3,3-difluorooctyl, 3,3-difluorononyl, 3,3-difluorodecyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-difluorohexyl, 4,4-difluoroheptyl, 4,4-difluorooctyl, 4,4-difluorononyl, 4,4-difluorodecyl, 5,5-difluoropentyl, 5,5-difluorohexyl, 5,5-difluoroheptyl, 5,5-difluorooctyl, 5,5-difluorononyl, 5,5-difluorodecyl, 6,6-difluorohexyl, 6,6-difluoroheptyl, 6,6-difluorooctyl, 6,6-difluorononyl, 6,6-difluorodecyl, 7,7-difluoroheptyl, 7,7-difluorooctyl, 7,7-difluorononyl, 7,7-difluorodecyl, 8,8-difluorooctyl, 8,8-difluorononyl, 8,8-difluorodecyl, 9,9-difluorononyl, 9,9-difluorodecyl or 10,10-difluorodecyl group.
    W, W1 and W2 independently denote H, F, Cl or CH3.
    X denotes a CN, F, Cl, CF3, CF2Cl, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, (O)5CY1=CX1X2 (X1 and Y1 denote H, F or Cl, and X2 denotes F or Cl), (O)sCpHqFr (p denotes 2, 3 or 4, and q and r are integers which satisfy the equation q+r = 2p +1, and s denotes 0 or 1), the aforementioned R or an alkyl or alkoxy group with 1-5 carbons.
    Y denotes H or F. Z denotes H or F.
    Specific examples of:
    Figure 00160001
    include the following groups:
    Figure 00160002
    Figure 00160003
    Figure 00170001
    Figure 00170002
    Figure 00170003
    Figure 00170004
    Figure 00170005
    Figure 00170006
    Figure 00170007
    Figure 00170008
    Figure 00180001
    (each n and m denote an integer of 0-9 where n + m is 1-9.),
    Figure 00180002
    Figure 00180003
    Figure 00180004
    Figure 00180005
    Figure 00180006
    Figure 00190001
    Figure 00190002
    Figure 00190003
    Figure 00190004
    Figure 00190005
    Figure 00190006
    Figure 00200001
    Figure 00200002
    Figure 00200003
    Figure 00200004
    Figure 00200005
    Figure 00200006
    Figure 00210001
    Figure 00210002
    Figure 00210003
    Figure 00210004
    Figure 00210005
    Figure 00220001
    Figure 00220002
    For R, 2-fluoroethyl, 2-fluoropropyl, 2-fluorobutyl, 2-fluoropentyl, 2-fluorohexyl, 2-fluoroheptyl, 4-fluorobutyl, 4-fluoropentyl, 4-fluorohexyl, 4-fluoroheptyl, 5-fluoropentyl, 5-fluorohexyl, 5-fluoroheptyl, 6-fluorohexyl, 6-fluoroheptyl, 5-fluoroheptyl, 2,2-difluoroethyl, 2,2-difluoropropyl, 2,2-difluorobutyl, 2,2-difluoropentyl, 2,2-difluorohexyl, 2,2-difluoroheptyl, 4,4-difluorobutyl, 4,4-difluoropentyl, 4,4-difluorohexyl, 4,4-difluoroheptyl, 5,5-difluoropentyl, 5,5-difluorohexyl, 5,5-difluoroheptyl, 6,6-difluorohexyl, 6,6-difluoroheptyl and 7,7-difluoroheptyl groups are desirable for practical use.
    H, F and CH2 groups are desirable for W in practical use. However, when the ring structure of the silacyclohexane ring is:
    Figure 00230001
    and X is a compound of CN, then W is limited to H or a CH3 group.
    For the group:
    Figure 00230002
    either group shown below is desirable:
    Figure 00230003
    Figure 00230004
    Figure 00230005
    Figure 00240001
    Figure 00240002
    Figure 00240003
    Figure 00240004
       (each n and m denotes an integer of 0-9 where 1 ≦ n + m ≦ 9.)
    Figure 00240005
    Figure 00240006
    Figure 00250001
    Figure 00250002
    Figure 00250003
    Figure 00250004
    Figure 00250005
    Figure 00250006
    Figure 00260001
    Figure 00260002
    Figure 00260003
    Figure 00260004
    Figure 00260005
    Figure 00270001
    Figure 00270003
    Figure 00270004
    The manufacturing methods of the compounds represented by the formula (I) are described next. (1) A method of preparing the compound of this invention when the ring structure of the silacyclohexane ring is:
    Figure 00280001
    and X is CN.
    In this preparation method, p-bromobenzene or p-iodobenzene with substitutional groups Y and Z is brought into reaction with magnesium in a solvent such as THF (tetrahydrofuran) to obtain the corresponding Grignard's reagent, which is then brought into reaction with a silacyclohexane compound whose silicon has the substitutional groups W and Q. The product is again brought into reaction with magnesium metal in a solvent such as THF (tetrahydrofuran) to prepare Grignard's reagent, which is then brought into reaction with a cyanogenation reagent such as cyanogen. The compound produced here is a mixture of trans isomers and cis isomers in terms of the configuration of the silacyclohexane ring. A conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (I). The reaction formula is shown below.
    Figure 00290001
    (P2 preferably denotes Br or I; X' denotes a halogen which is preferably Cl, Br or I; and Q denotes a halogen or an alkoxy group with preferably 1-4 carbons.) (2) A method of preparing the compound of this invention other than (1) as described above.
    Although the reaction substrates are somewhat different depending on the ring structure, all of them are prepared using the coupling reactions of organometallic reagents shown below.
    In this preparation method, R-halide or substituted aryl halide is used in a solvent such as THF (tetrahydrofuran) to obtain the corresponding organometallic reagent. The organometallic reagent thus produced is then brought into reaction with a silacyclohexane compound whose silicon has the substitutional groups W and Q. The compound produced here is a mixture of trans isomers and cis isomers in terms of the configuration of the silacyclohexane ring. A conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (I). The reaction formula is shown below.
    Figure 00300001
    Figure 00310001
    {M denotes MgP1 (P1 denotes a halogen which is preferably Cl, Br or I), ZnP1 or Li; M' denotes Mg (P2 preferably denotes Br or I (when X is Cl), or Cl, Br or I (when X is not Cl)). ZnP2 or Li; Q denotes a halogen or alkoxy group with preferably 1-4 carbons; and W denotes a H, F, Cl or CH3 group. X denotes a CN, F, Cl, CF3, CF2Cl, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, (O)sCY1=CX1X2 (X1 and Y1 denote H, F or Cl, and X2 denotes F or Cl), (O)sCpHqFr (p denotes 2, 3 or 4, and q and r are integers which satisfy the equation q+r = 2p +1, and s denotes 0 or 1), R or an alkyl or alkoxy group with 1-5 carbons. Y denotes H or F. Z denotes H or F. If W = F or Cl, then W = Q. }
    The manufacturing methods of the compounds represented by the formula (II) are described next. Although the reaction substrates are somewhat different depending on the ring structure, all of them are prepared using the organometallic coupling reactions shown below.
    Figure 00320001
    Figure 00320002
    Figure 00320003
    P1 denotes a halogen which is preferably Cl, Br or I; Q denotes a halogen or an alkoxy group with preferably 1-4 carbons, M: MgP (P denotes a halogen), ZnP or Li, (If W = F or Cl, or W2 = F or Cl, then W = Q, W2 = Q, and W1 ≠ F or Cl)
    In the preparation method described above, a cyclohexyl halide, R-halide or silacyclohexyl halide in a solvent such as THF (tetrahydrofuran) is used in a conventional manner to obtain the corresponding organometallic reagent. When doing this, an appropriate metal species is chosen according to the type of the substitutional group X. The metal halide thus produced is then brought into reaction with a silacyclohexane compound whose silicon has the substitutional groups W or W2 and Q. The compound produced here is a mixture of trans isomers and cis isomers in terms of the conformation of the silacyclohexane ring. A conventional purification means such as chromatography and recrystallization is employed to separate and purify the trans isomers to obtain the silacyclohexane compound of this invention represented by the general formula (II).
    The silacyclohexane compound of this invention can be mixed with known compounds to obtain a liquid crystal composition. The compound used for mixing to obtain the liquid crystals compound can be chosen from among the known compounds shown below:
    Figure 00340001
    Figure 00340002
    In the above formulas, (M) and (N) denote one of the following:
  • 1) A trans-1,4trans-1,4-cyclohexylene group which has no substitution or which has one or more substitutional groups such as F, Cl, Br, CN or alkyl groups;
  • 2) A ring comprising a cyclohexane ring in which O or S is substituted for one or nonadjacent two CH2 groups;
  • 3) A 1,4-cyclohexenylene group;
  • 4) A 1,4-phenylene group which has no substitution or which has one or two substitutional groups chosen from among F, Cl, CH3 and CN groups; or
  • 5) A ring comprising a 1,4-phenylene group in which an N atom is substituted for one or two CH groups.
    • Z1 and Z2 denote -CH2CH2-, -CH=CH-, -C ≡ C-, -CO2-, -OCO-, -CH2O-, -OCH2- or a single bond.
    ℓ, m = 0, 1 or 2 (where ℓ + m = 1, 2 or 3, and n = 0, 1 or 2)
    R' denotes hydrogen, a linear-chain alkyl group with 1-10 carbons, a branched-chain alkyl group with 3-8 carbons, an alkoxyalkyl group with 2-7 carbons, a mono- or di- fluoroalkyl group with 1-10 carbons or an alkenyl group with 2-8 carbons.
    X, Y and Z are the same as defined for the general formulas (I) or (II).
    In the above description, if ℓ or n = 2, then (M) can contain heterogeneous rings, and if m = 2, then (N) can contain heterogeneous rings.
    The ratio of one or more types of the silacyclohexane compound of this invention contained in the liquid crystal composition is 1-50 mol%, more preferably 5-30 mol%. The liquid crystal composition can also contain a polygenetic dye(s) to generate the colored guest-host system and additives to change the dielectric anisotropy, viscosity and the orientation of the nematic phase.
    The liquid crystal composition thus formed can be used to manufacture various liquid crystal display elements in conventional methods. That is, the liquid crystal composition containing the silacyclohexane compound of this invention is sealed between transparent plates which have electrodes of desired shapes and thus used as liquid crystal display elements. This element can have various undercoatings, overcoatings for the orientation control, a polarizer plate(s), a filter(s) and a reflector layer(s), as necessary. It can be made into a laminated cell or combined with other display elements. Semiconductor substrates and light sources can also be used to make various types of displays.
    For the driving method of the liquid crystal display element, prior-art methods in the industry of liquid crystal display elements, such as the dynamic scattering (DSM) method, the twisted nematic (TN) method, the guest-host (GH) method, the super twisted nematic (STN) method and the polymer dispersion liquid crystal (PDLC) method can be adopted.
    The silacyclohexane compounds of this invention have a strong tendency to show an enantiotropic phase transition when their substitutional group X is CN. When the substitutional group X is not CN, most of them show a monotropic phase transition or a crystal-isotropic liquid type transition, and do not show the electro-optical characteristics of liquid crystals when used separately. However, they contribute to a reduction in the viscosity and a lowering of the melting point when used with other liquid crystal compounds in a liquid crystal composition.
    By using the liquid crystal compounds of this invention which have Si as a ring composing element as components of a liquid crystal composition, reduction of the viscosity, improvement of the response time and improvement of compatibility in low temperatures can be achieved.
    Also, liquid crystal compounds whose X in the general formula (I) is neither R nor OR have, in addition to the advantages mentioned above, an effect of lowering the threshold voltage because of a greater dielectric anisotropy.
    The liquid crystal compound whose substitutional group X in the general formula (I) is an alkyl group, an alkoxyalkyl group, R or OR has near-zero negative dielectric anisotropy, and therefore it should preferably be used for the liquid crystal phase for display based on the dynamic scattering (DS) or deformation of aligned phase (DAP mode). The compounds in which X is other than an alkyl group, an alkoxyalkyl group, R or OR should preferably be used for manufacturing the liquid crystal phase with a large positive dielectric anisotropy which is used in display elements based on the twisted nematic cell or the cholesteric-nematic phase transition.
    The liquid crystal compounds of the present invention which have Si as a ring composing element have the following advantages over liquid crystal compounds which have a conventional CCP structure comprising similar hydrocarbon rings:
  • (1) Because they have the nematic liquid crystal phase extended to lower temperatures, the following low temperature characteristics improve.
  • (2) The viscosity in a low temperature range drops, resulting in the improved response time in the low temperature range.
  • (3) Compatibility in a low temperature range improves.
    • Also, liquid crystal compounds whose X in the general formula (II) is neither R nor OR have, in addition to the advantages mentioned above, an effect of lowering the threshold voltage.
    The threshold voltage can be lowered by increasing the dielectric anisotropy (Δε) of the liquid crystal compound. The compounds of the present invention have an advantage of having a lower threshold voltage compared with the prior art compounds with the same Δε.
    The liquid crystal compounds of this invention, depending on the selection of their substitutional groups, can be widely used as the base material which comprises the major component of the liquid crystal phase, in a manner similar to how the conventional liquid crystal compounds with a CCP structure of similar hydrocarbon rings are used. The liquid crystal compound whose substitutional group X in the general formula :
    Figure 00390001
    is R or OR has near -zero dielectric anisotropy, and therefore it should preferably be used for the liquid crystal phase for display based on the dynamic scattering (DS) or deformation of aligned phase (DAP mode). The compounds in which X is other than R or OR should preferably be used for manufacturing the liquid crystal phase with a large positive dielectric anisotropy which is used in display elements based on the twisted nematic cell or the cholesteric-nematic phase transition.
    Examples
    The details of this invention are described below by referring to specific examples.
    [Example 1] Preparation of 4-(trans-4-n-(4-fluoropentyl)-4-silacyclohexyl) benzonitrile
    3.4 g (20 mmol) of 1-bromo-4-fluoropentane was dripped into a mixture of 0.5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This solution was then added to a mixture of 2.8 g of zinc chloride and 20 ml of THF to obtain the organic zinc reagent. This solution was then dripped into a 50 ml THF solution of 4.7 g (20 mmol) of 4 -(4-chloro-4-silacyclohexyl) benzonitrile to obtain 4-(4-(4-fluoropentyl)-4-silacyclohexyl) benzonitrile.
    This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 5.3 g of the trans isomers (yield 92%).
    [Example 2] Preparation of 4-(trans-4-(7-fluoroheptyl)-4-silacyclohexyl)-1,2-difluorobenzene
    3.0 g (20 mmol) of 1-bromo-7-fluoroheptane was dripped into a mixture of 0.5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This reagent was then dripped into a 50 ml THF solution of 4.9 g (20 mmol) of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene to obtain 4-(4-(7-fluoroheptyl)-4-silacyclohexyi)-1,2-difluorobenzene.
    This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 6.1 g of the trans isomers (yield 93%).
    [Example 3] 4-(trans-4-(4-fluoroheptyl)-4-silacyclohexyl)-1-fluorobenzene
    The above compound was obtained in the same manner as Example 2, using 4-(4-chloro-4-silacyclohexyl)-1-fluorobenzene instead of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, with 1-bromo-7-fluoroheptane. IR (liquid film) ν max: 2920, 2873, 2100, 1510, 1227, 985, 887 and 820 cm-1.
    C-N transition temperature: 27°C
    [Example 4] 4-(trans-4-(4-fluoroheptyl)-4-silacyclohexyl)-1-chlorobenzene
    The above compound was obtained in the same manner as Example 2, using 4-(4-chloro-4-silacyclohexyl)-1-fluorobenzene instead of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, with 1-bromo-7-fluoroheptane.
    [Example 5] 4-(trans-4-methoxypentyl-1-silacyclohexyl)-1-difluoromethoxybenzene
    The above compound was obtained in the same manner as Example 2, using 4-(4-chloro-4-silacyclohexyl)-1-fluoromethoxybenzene instead of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, with 1-bromo-7-fluoroheptane.
    The compounds of this invention obtained in the examples described above were added to existing liquid crystal compositions to prepare liquid crystal compositions of this invention. For the obtained liquid crystal compositions, the threshold voltage and the viscosity at 20 °C were measured.
    [Example 6] Preparation of 4-(trans-4-(trans-4-(4-fluorobutyl) cyclohexyl-4-silacyclohexyl)-1, 2-difluorobenzene
    4. 7 g (20 mmol) of 4-(4-fluorobutyl) cyclohexyl bromide was dripped into a mixture of 0.5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This solution was then dripped into a 50 ml THF solution of 4.9 g (20 mmol) of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene to obtain 4-(4-(trans-4-n-propylcyclohexyl)-4-silacyclohexyl)-1,2-difluo robenzene. This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 6. 7 g of the trans isomers (yield 91%).
    [Example 7] 4-(trans-4-(trans-4-(4,4-difluorobutyl) cyclohexyl)-4-silacyclohexyl)-1-fluorobenzene
    The above compound was obtained in the same manner as Example 6, using 4-(4,4-difluorobutyl)cyclohexylibromide and 4-(4-chloro-4-silacyclohexyl)-1-fluorobenzene instead of 4-(4-fluorobutyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
    [Example 8] 4-(trans-4-(trans-4-(4,4-difluorobutyl) cyclohexyl)-4-silacyclohexyl)-1-chlorobenzene
    The above compound was obtained in the same manner as Example 6, using 4-(4,4-difluorobutyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-chlorobenzene instead of 4-(4-fluorobutyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
    [Example 9] 4-(trans-4-(trans-4-(4-fluoropentyl) cyclohexyl)-4-silacyclohexyl)-1-trifluoromethoxybenzene
    The above compound was obtained in the same manner as Example 6, using 4-(4-fluoropentyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethoxybenzene instead of 4-(4-fluorobutyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
    [Example 10] 4-(trans-4-(trans-4-(4-fluorobutyl) cyclohexyl)-4-silacyclohexyl)-1,2,6-trifluorobenzene
    The above compound was obtained in the same manner as Example 6, using 4-(4-chloro-4-silacyclohexyl)-1,2,6-trifluorobenzene instead of 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, with 4-(4-fluorobutyl) cyclohexylbromide.
    [Example 11]
    4-(trans-4-methyl-4-(trans-4-(3-fluoropropyl) cyclohexyl) -4-silacyclohexyl)-1-methoxybenzene
    The above compound was obtained in the same manner as Example 6, using 4-(3-fluoropropyl)cyclohexylbromide and 4-(4-chloro-4-methyl-4-silacyclohexyl)anisole instead of 4-(4-fluorobutyl)cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
    [Example 12] 4-(trans-4-methyl-4-(trans-4-(3-fluoropropyl) cyclohexyl) -4-silacyclohexyl)-1-chloro-2,6-difluorobenzene
    The above compound was obtained in the same manner as Example 6, using 4-(3-fluoropropyl)cyclohexylbromide and 4-(4-chloro-4-methyl-4-silacyclohexyl)-1-chloro-2,6-difluorobenzene instead of 4-(4-fluorobutyl) cyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1,2-difluorobenzene, respectively.
    [Example 13] 4-(trans-4-(trans-4-(4-fluorobutyl) cyclohexyl)-4-silacyclohexyl) benzonitrile
    4.7 g (20 mmol) of 4-(4-fluorobutyl) cyclohexyl bromide was dripped into a mixture of 0.5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This solution was then added to a mixture of 3.0 g (22 mmol) of zinc chloride and 10 ml of THF to obtain the organic zinc reagent. This reagent was then dripped into a 50 ml THF solution of 4.7 g (20 mmol) of 4-(4-chloro-4-silacyclohexyl) benzonitrile to obtain 4-(4-(trans-4-n-propylcyclohexyl)-4-silacyclohexyl) benzonitrile. This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 5. 9 g of the trans isomers (yield 83%).
    [Example 14] 4-(trans-4-(trans-4-(4-fluoropentyl)-4-silacyclohexyl) cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene
    3.4 g (20 mmol) of 4-fluoropentyl bromide was dripped into a mixture of 0. 5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This solution was then dripped into a 50 ml THF solution of 7.9 g (20 mmol) of 4-(4-(4-chloro-4-silacyclohexyl)trans-4-cyclohexyl)-1-difluoroaethoxy-2,6-difluorobenzene to obtain 4-(trans-4-(trans-4-n-pentyl-4-silacyclohexyl)-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene. This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chroma- tography to obtain 7.4 g of the trans isomers (yield 90%).
    [Example 15] 4-(trans-4-(trans-4-(3-fluoropropyl)-4-silacyclohexyl) cyclohexyl)-1-fluorobenzene
    The above compound was obtained in the same manner as Example 14, using 3-fluoropropylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-fluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
    [Example 16] 4-(trans-4-(trans-4-(4-fluorobutyl)-4-silacyclohexyl) cyclohexyl)-1,2-difluorobenzene
    The above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-fluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2, 6-difluorobenzene, respectively. IR (liquid film) ν max: 2924, 2852, 2100, 1518, 1277, 1207, 987, 887 and 822 cm-1
    C-N transition temperature: 11°C, N-I transition temperature: 67°C
    [Example 17] 4-(trans-4-(trans-4-(4-fluorobutyl)-4-silacyclohexyl)-4-cyclohexyl)-1-trifluoromethoxybenzene
    The above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-trifluoromethoxybenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively. IR (KBr disc) ν max: 2924, 2852, 2110, 1510, 1265, 1221, 1192, 1161, 985, 887 and 827 cm-1
    C-N transition temperature: 43°C, N-I transition temperature: 97°C, S-N transition tem- perature: 32°C
    [Example 18] 4-(trans-4-(trans-4-(3-fluoropropyl)-4-silacyclohexyl) cyclohexyl)-1-chloro-2-fluorobenzene
    The above compound was obtained in the same manner as Example 14, using 3-fluoropropylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-chloro-2-fluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
    [Example 19] 4-(trans-4-(trans-4-(4-fluorobutyl)-4-silacyclohexyl) cyclohexyl)-2,3-difluoro-1-ethoxybenzene
    The above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-2,3-difluoro-1-ethoxybenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
    [Example 20] 4-(trans-4-(trans-4-(3-fluoropropyl)-4-silacyclohexyl) cyclohexyl)-1-(4-fluorobutyl) benzene
    The above compound was obtained in the same manner as Example 14, using 1-bromopropane and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-(4-fluorobutyl)benzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene, respectively.
    [Example 21] 4-(trans-4-(trans-4-(4-fluorobutyl)-4-silacyclohexyl) cyclohexyl)-1-difluoromethoxy-2, 6-difluorobenzene
    The above compound was obtained in the same manner as Example 14, using 4-fluorobutylbromide and 4-(4-(4-chloro-4-silacyclohexyl)-trans-4-cyclohexyl)-1-difluoromethoxy-2,6-difluorobenzene instead of 4-fluoropentylbromide and 4-(4-(4-chloro-4-silacyclohexyl)trans-4-cyclohexyl)-1-difluoroaethoxy-2,6-difluorobenzene, respectively.
    IR (KBr disc) ν max: 2927, 2856, 2106, 1516, 1146, 1097, 1065, 1034, 889 and 812 cm-1
    C-N transition temperature: 52°C, N-I transition temperature: 80°C
    [Example 22] 4-(trans-4-(trans-4-(4,4-difluorobutyl)-4-silacyclohexyl)-4-silacyclohexyl)-1-trifluoromethylbenzene
    5. 4 g (20 mmol) of 4-(4, 4-difluorobutyl) silacyclohexyl bromide was dripped into a mixture of 0. 5 g of magnesium (21 mmol) and 50 ml of THF to obtain Grignard's reagent. This solution was then dripped into a 50 ml THF solution of 5. 6 g (20 mmol) of 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethylbenzene to obtain 4-(4-(4-n-propylsilacyclohexyl)-4-silacyclohexyl)-1-trifluorom ethylbenzene. This product was a mixture of trans isomers and cis isomers with regard to the silacyclohexane ring. They were separated by means of chromatography to obtain 7.4 g of the trans isomers (yield 85%).
    [Example 23] 4-(trans-4-(trans-4-(3-fluoropropyl)-4-silacyclohexyl)-4-silacyclohexyl)-1-n-propylbenzene
    The above compound was obtained in the same manner as Example 23, using 4-(3-fluoropropyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-n-propylbenzene instead of 4-(4, 4-difluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethoxybenzene, respectively.
    [Example 24] 4-(trans-4-(trans-4-(4-fluorobutyl)-4-methyl-4-silacyclohexyl) -1-trifluoromethoxy-2-fluorobenzene
    The above compound was obtained in the same manner as Example 23, using 4-(4-fluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-methyl-4-silacyclohexyl)-1-trifluoromethoxy-2-fluorobenzene instead of 4-(4,4-difluorobutyl)-4-silacyclohexylbromide and 4-(4-chloro-4-silacyclohexyl)-1-trifluoromethoxybenzene, respectively.
    The compounds of this invention obtained in the examples described above were added to existing liquid crystal compositions to prepare liquid crystal compositions of this invention. For the obtained liquid crystal compositions, the threshold voltage and the transition temperature were measured.
    [Example of the liquid crystal composition]
    A mixture A which comprises 40 moles of 4-(4-(trans-4-ethylcyclohexyl) -trans-4-cyclohexyl)-1, 2-difluor obenzene, 35 mol% of 4-(4-(trans-4-n-propylcyclohexyl)-trans-4-cyclohexyl)-1,2-difluorobenzene and 25 mol% of 4-(4-(trans-4-n-pentylcyclohexyl)-trans-4-cyclohexyl)-1,2-difluorobenzene exhibits characteristics listed below.
    C-N transition temperature: 7°C
    N-I transition temperature: 106°C
    Threshold voltage: 2.50 V
    A mixture which comprises 80% of this mixture A and 20 mol% of 4-(trans-4-(trans-4-(4-fluorobutyl)-4-silacyclohexyl) cyclohexyl)-1-trifluoromethoxybenzene from Example 12 exhibited characteristics listed below.
    C-N transition temperature: 0°C
    N-I transition temperature: 104°C
    Threshold voltage: 2.34 V

    Claims (9)

    1. A silacyclohexane compound represented by the following general formula (I):
      Figure 00530001
         wherein
      R denotes a mono- or di-fluoroalkyl group with 1-10 carbons;
      Figure 00530002
      denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3;
      X denotes a CN, F, Cl, CF3, CF2Cl, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, (O)sCY1=CX1X2 (X1 and Y1 denote H, F or Cl, and X2 denotes F or Cl), (O)sCpHqFr (p denotes 2, 3 or 4, and q and r are integers which satisfy the equation q+r = 2p +1, and s denotes 0 or 1), the aforementioned R, or an alkyl or alkoxy group with 1-5 carbons;
      Y denotes H or F; and
      Z denotes H or F.
    2. A method of preparing the silacyclohexane compound as described in Claim 1 characterized by the use of a reaction between an organometallic reagent R-M (f denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound:
      Figure 00540001
      wherein W denotes H, F, Cl or a CH3 group, and Q denotes a halogen or an alkoxy group.
    3. A method of preparing the silacyclohexane compound as described in Claim 1 characterized by the use of a reaction between an organometallic reagent:
      Figure 00540002
      and a silacyclohexane compound:
      Figure 00550001
    4. A method of preparing the silacyclohexane compound as described in Claim 1 wherein X is CN, characterized by the use of a reaction between an organometallic reagent:
      Figure 00550002
      (M denotes MgP' (P' denotes Br or I), ZnP' or Li, and X' denotes a halogen) and a silacyclohexane compound:
      Figure 00550003
      to obtain a phenylsilacyclohexane compound:
      Figure 00550004
      from which a Grignard's reagent is made, which is then reacted with a cyanogenation agent.
    5. A silacyclohexane compound represented by the following general formula (II):
      Figure 00560001
      wherein R denotes hydrogen or a mono- or di-fluoroalkyl group with 1-10 carbons;
      at least one of
      Figure 00560002
      and
      Figure 00560003
      denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3 and the other denotes a trans-1,4-cyclohexylene group, a trans-1-sila-1,4-cyclohexylen group or a trans-4-sila-1,4-cyclohexylene group;
      X denotes a CN, F, Cl, CF3, CF2CI, CHFCl, OCF3, OCHF2, OCF2Cl, OCHFCl, the aforementioned R, or an alkyl or alkoxy group with 1-5 carbons;
      Y denotes H or F; and
      Z denotes H or F.
    6. A method of preparing the silacyclohexane compound as described in Claim 5 characterized by the use of a reaction between an organometallic reagent R-M (M denotes MgP (P denotes a halogen), ZnP or Li) and a silacyclohexane compound:
      Figure 00570001
      wherein W denotes H, F, Cl or a CH3 group, and Q denotes a halogen or an alkoxy group.
    7. A method of preparing the silacyclohexane compound as described in Claim 5 characterized by the use of a reaction between an organometallic reagent:
      Figure 00580001
      and a silacyclohexane compound:
      Figure 00580002
         wherein
      Figure 00580003
      denotes a trans-1-silacyclohexylene or a trans-4-silacyclohexylene group whose silicon at position 1 or position 4 has a substitutional group of H, F, Cl or CH3, or a cyclohexylene group;
      W denotes H, F, Cl or a CH3 group; and
      Q denotes a halogen or an alkoxy group.
    8. A liquid crystal composition characterized by containing the silacyclohexane compound as described in Claim 1 or 5.
    9. A liquid crystal display element characterized by containing the liquid crystal composition as described in Claim 8.
    EP95120442A 1994-12-22 1995-12-22 A silacyclohexane compound, a method of preparing it and a liquid crystal composition containing it Expired - Lifetime EP0718301B1 (en)

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